Production process of olefin based polymers

ABSTRACT

A process for effectively producing an alpha-olefin homopolymer or copolymer of two or more of alpha-olefins without using a great amount of an aluminum compound, is disclosed. In the process for producing a cyclic olefin based polymer according to the present invention, homopolymerization of an alpha-olefin or copolymerization of two or more of alpha-olefins is effected in the presence of a catalyst comprising, as main ingredients, the following Compounds (A), (B) and (C): 
     (A) a transition metal compound; 
     (B) a compound capable of forming an ionic complex when reacted with a transition metal compound; and 
     (C) an organoaluminum compound.

TECHNICAL FIELD

The present invention relates to a production process of an olefin basedpolymer, and more particularly to a process for effectively producing ahomopolymer of an alpha-olefin or a copolymer of two or more ofalpha-olefins.

BACKGROUND ART

Heretofore, the Kaminsky type catalysts containing a transition metalcompound and aluminoxane have been known as a soluble olefinpolymerization catalyst. For example, the following catalysts are known.In the alpha-olefin polymerization, a catalyst composed of a zirconiumcompound and aluminoxane shows high polymerization activity (JapanesePatent Application Unexamined Publication No. Sho 58-19309).Stereo-regular polypropylene is produced using a catalyst composed of azirconium compound having a ligand in which two indenyl groups areconnected through an ethylene group, and aluminoxane (JP Pat. Appln.Unexamined Pub. No. Sho 61-130314). It is said that using these Kaminskytype catalysts, for example in the propylene polymerization, any ofisotactic polypropylene, atactic polypropylene and syndiotacticpolypropylene can be produced (Macromol. Chem., Rapid Commun. 4,417-421(1983); Angew. Chem. Int. Ed. Engl. 24,507-508 (1985); J. Am. Chem. Soc.109,6544-6545 (1987); and J. Am. Chem. Soc. 110,6255-6256 (1988)).

In this case, as a transition metal compound useful for producingisotactic polypropylene, a transition metal compound having an ethylenebis(indenyl) ligand (JP Pat. Appln. Unexamined Pub. No. Sho 61-264010;Sho 64-51408; and Sho 64-66216); R(C₅ (R')₄)₂ MeQp type metallocenecompound reported by Ewen et al (JP Pat. Appln. Unexamined Pub. No. Sho63-251405; Sho 63-295607; and Sho 64-74202); a metallocene compoundcross-linked with silicon or the like (JP Pat. Appln. Unexamined Pub.No. Hei 3-12406); and the like are known. Further, a metallocenecompound useful for producing a stereo-block polymer is known (JP Pat.Appln. Unexamined Pub. No. Sho 63-142004 and Sho 63-2005).

However, the above-mentioned polymerization methods require use of agreat amount of expensive aluminoxane which is 100 to 10,000 times theamount of a transition metal compound to obtain sufficient activity.Further, due to use of a great amount of aluminoxane, a substantialamount of metal will remain in the polymerized products, resulting indeterioration and coloring of the products. In these processes, afterpolymerization, deashing treatment of the resultant products should besufficiently conducted. Thus, these processes have a problem inproductivity.

Further, aluminoxane is produced from the reaction of highly reactivetrimethylaluminum and water, leading to risks. Furthermore, the reactionproduct is a mixture of several materials containing unreactedmaterials, and it is quite difficult to isolate one single substance.Thus, management of catalysts to obtain a product having stable physicalproperties is quite difficult.

On the other hand, JP Pat. Appln. PCT Pub. No. Hei 1-502036 discloses apolymerization process for producing an alpha-olefin polymer using, as acatalyst, a specific boron complex containing ammonium and a metallocenecompound. However, the catalyst shows extremely low polymerizationactivity and thus is not suitable for industrial use.

Further, syndiotactic polyolefins, particularly syndiotacticpolypropylene (SPP) are known. However, there are some problems in allconventional processes for producing syndiotactic polyolefins.

For example, it is known that SPP can be produced at -78° C. using acatalyst system composed of VCl₄, anisole and dibutylaluminum chloride(By B. Lotz et al, Macromolecules 21, 1988, 2375). However, thepolymerization temperature is extremely low. Also, the stereo-regularityof the resultant product and the yield are extremely low.

Further, it is known that SPP can be obtained, at a drastically improvedyield, at 25° to 70° C. using a catalyst composed ofisopropylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride andmethylaluminoxane (By J. A. Ewen et al., J. Am. Chem. Soc., 110, 1988,6255). However, the SPP obtained in this process has low molecularweight.

Further, it is known that SPP having high molecular weight can beproduced using[phenyl(methyl)methylene](9-fluorenyl)(cyclopentadienyl)zirconiumdichloride or diphenylmethylene(9-fluorenyl)(cyclopentadienyl)zirconiumdichloride, and methylaluminoxane (JP Pat. Appln. Unexamined Pub. No.Hei 2-274703). However, in this process, a great amount of expensivealuminoxane against a transition metal compound should be employed.

Accordingly, a process for producing syndiotactic polyolefin in anindustrially effective way at high yield, has not yet been found.

DISCLOSURE OF THE INVENTION

The present invention was made in view of the above-mentionedsituations, and has an object of providing a process for effectivelyproducing a homopolymer of an alpha-olefin or a copolymer of two or moreof alpha-olefins without using a great amount of an organoaluminumcompound.

To achieve the above object, the present invention provides a processfor producing an olefin based polymer wherein homopolymerization of analpha-olefin or copolymerization of alpha-olefins is carried out in thepresence of a catalyst comprising, as main components, the followingcompounds (A), (B) and (C):

(A) a transition metal compound;

(B) a compound capable of forming an ionic complex when reacted with atransition metal compound; and

(C) an organoaluminum compound.

In this case, if the following compound (A1) is used as Compound (A),olefin based polymers can be effectively produced, without using aspecial compound, on an industrial scale. Transition metal compoundrepresented by the following Formula (A1):

    M.sup.1 R.sup.1 aR.sup.2 bR.sup.3 cR.sup.4 d

wherein M¹ is a transition metal; R¹, R², R³ and R⁴ may be the same asor different from each other, and are independently a ligand having asigma bond, chelate ligand or Lewis base; and a, b, c and d areindependently an integer of 0 to 4.

Further, olefin based polymers can be produced using a catalyst onlycomprising this compound (A1) and the above-mentioned Compound (B) asmain components.

Furthermore, if the following compound (A2) is used as Compound (A),high-molecular-weight syndiotactic polyolefins having highsyndiotacticity can be effectively produced without using a great amountof an organoaluminum compound. Transition metal compound (A2)represented by the following Formula:

    (Cp.sup.1 --Ae--Cp.sup.2)M.sup.1 R.sup.1 fR.sup.2 g

wherein Cp¹ is a cyclopentadienyl group or substituted cyclopentadienylgroup; Cp² is a fluorenyl group or substituted fluorenyl group; A is abridge based on a covalent bond, and each A may be the same or differentfrom each other; e is an integer of 0 to 6; M¹ is a transition metalselected from the IVB Group of the Periodic Table; R¹ and R² may be thesame as or different from each other, and are independently a ligandhaving a sigma bond, chelate ligand or Lewis base; and f and g areindependently an integer of 0 to 2.

In addition, a catalyst for olefin polymerization comprising, a specificmetallocene catalyst containing a cyclopentadienyl group and alkylaluminum has been proposed (EPC Publication No. 0426638; JP Pat. Appln.Unexamined Pub. No. Hei 3-207704). However, the catalysts disclosed inthe above publications are different from those used in the presentinvention in that a transition metal compound is limited to a dialkylmetallocene compound containing a biscyclopentadienyl group; aluminumcompound are limited to trimethyl aluminum and triethylaluminum; andaluminoxane is excluded from aluminum compound used.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the flowchart of the production process of the presentinvention; and

FIGS. 2 and 3 are each a NMR chart showing the measurement result of thepolymer obtained in the example.

BEST EMBODIMENTS FOR CARRYING OUT THE INVENTION

The present invention will be described in more detail below. Inaddition, FIG. 1 shows the production process according to the presentinvention.

In the present invention, a transition metal compound is used asCompound (A). The transition metal compounds include, for example, thosecontaining a transition metal belonging to the IVB, VB, VIB, VIIB andVIII Groups of the Periodic Table. More specifically, as the abovetransition metals, preferred are titanium, zirconium, hafnium, chromium,manganese, nickel, palladium and platinum. Of these, more preferred arezirconium, hafnium, titanium, nickel and palladium.

These transition metal compounds include a variety of compounds,particularly include those containing a transition metal belonging tothe IVB and VIII Groups of the Periodic Table, more suitably atransition metal of the IVB Group, i.e., titanium (Ti), zirconium (Zr)or hafnium (Hf). More preferred are cyclopentadienyl compoundsrepresented by the following Formula (I), (II) or (III), or derivativesthereof, or compounds represented by the following Formula (IV) orderivatives thereof.

    CpM.sup.1 R.sup.1 aR.sup.2 bR.sup.3 c                      (I)

    Cp.sub.2 M.sup.1 R.sup.1 aR.sup.2 b                        (II)

    (Cp--Ae--Cp)M.sup.1 R.sup.1 aR.sup.2 b                     (III)

    M.sup.1 R.sup.1 aR.sup.2 bR.sup.3 cR.sup.4 d               (IV)

In Formulas (I) to (IV), M¹ is a Ti, Zr or Hf atom; Cp is a groupcontaining an unsaturated cyclic hydrocarbon group such as acyclopentadienyl group, substituted cyclopentadienyl group, indenylgroup, substituted indenyl group, tetrahydroindenyl group, substitutedtetrahydroindenyl group, fluorenyl group or substituted fluorenyl group;R¹, R², R³ and R⁴ are independently a hydrogen atom, oxygen atom,halogen atom, C₁₋₂₀ alkyl group, C₁₋₂₀ alkoxy group, C₆₋₂₀ aryl group,C₆₋₂₀ aryloxy group alkylaryl group or arylalkyl group, C₁₋₂₀ acyloxygroup, allyl group, substituted allyl group, a ligand having a sigmabond such as a substituent containing a silicon atom, chelate ligandsuch as an acetylacetonate group and substituted acetylacetonate groupor Lewis base ligand; A is a bridge based on a covalent bond, and may bethe same as or different from each other; a, b, c and d areindependently an integer of 0 to 4; e is an integer of 0 to 6; and twoor more of R¹, R², R³ and R⁴ may form a ring. If the above-mentioned Cphas any substituent, the substituent is preferably a C₁₋₂₀ alkyl group.In Formulas (II) and (III), two of Cp may be the same as or differentfrom each other.

In the above Formulas (I) to (III), the substituted cyclopentadienylgroups include, for example, a methylcyclopentadienyl group,ethylcyclopentadienyl group, isopropylcyclopentadienyl group,1,2-dimethylcyclopentadienyl group, tetramethylcyclopentadienyl group,1,3-dimethylcyclopentadienyl group, 1,2,3-trimethylcyclopentadienylgroup, 1,2,4-trimethylcyclopentadienyl group, pentamethylcyclopentadieylgroup and trimethylsilylcyclopentadienyl group. Examples of R¹ to R⁴ inthe above Formulas (I) to (IV), include halogen atoms such as a fluorineatom, chlorine atom, bromine atom and iodine atom; C₁₋₂₀ alkyl groupssuch as a methyl group, ethyl group, n-propyl group, isopropyl group,n-butyl group, octyl group and 2-ethylhexyl group; C₁₋₂₀ alkoxy groupssuch as a methoxy group, ethoxy group, propoxy group, butoxy group:C₆₋₂₀ aryloxy groups such as a and phenoxy group; C₆₋₂₀ aryl groups,alkylaryl groups or arylalkyl group, such as a phenyl group, tolylgroup, xylyl group and benzyl group; C₁₋₂₀ acyloxy groups such as aheptadecylcarbonyloxy group; substituents containing a silicon atom suchas a trimethylsilyl group and (trimethylsilyl)methyl group; Lewis basessuch as ethers including dimethyl ether, diethyl ether andtetrahydrofuran, thioethers including tetrahydrothiophen, estersincluding ethylbenzoate, nitriles including acetonitrile andbenzonitrile, amines including trimethylamine, triethylamine,tributylamine, N, N-dimethylaniline, pyridine, 2,2'-bipyridine andphenantholorine, and phosphines including triethylphosphine andtriphenylphosphine; chain unsaturated hydrocarbons such as ethylene,butadiene, 1-pentene, isoprene, pentadiene, 1-hexene unsaturated cyclichydrocarbons such as benzene, toluene, xylene, cycloheptatriene,cyclooctadiene, cyclooctatriene, cyclooctatetraene and derivativesthereof. The bridges based on a covalent bond, A in the above Formula(III) include, for example, a methylene bridge, dimethylmethylenebridge, ethylene bridge, 1,1'-cyclohexylene bridge, dimethylsilylenebridge, dimethylgelmylene bridge and dimethylstannylene bridge.

More specifically, these compounds include the following compounds, andthose having titanium or hafnium instead of zirconium.

Compounds of Formula (I):

(Pentamethylcyclopentadienyl)trimethylzirconium,

(pentamethylcyclopentadienyl)triphenylzirconium,

(pentamethylcyclopentadienyl)tribenzylzirconium,

(pentamethylcyclopentadienyl)trichlorozirconium,

(pentamethylcyclopentadienyl)trimethoxyzirconium,

(cyclopentadienyl)trimethylzirconium,

(cyclopentadienyl)triphenylzirconium,

(cyclopentadienyl)tribenzylzirconium,

(cyclopentadienyl)trichlorozirconium,

(cyclopentadienyl)trimethoxyzirconium,

(cyclopentadienyl)dimethyl(methoxy)zirconium,

(methylcyclopentadienyl)trimethylzirconium,

(methylcyclopentadienyl)triphenylzirconium,

(methylcyclopentadienyl)tribenzylzirconium,

(methylcyclopentadienyl)trichlorozirconium,

(methylcyclopentadienyl)dimethyl(methoxy)zirconium,

(dimethylcyclopentadienyl)trichlorozirconium,

(trimethylcyclopentadienyl)trichlorozirconium,

(trimethylsilylcyclopentadienyl)trimethylzirconium,

(tetramethylcyclopentadienyl)trichlorozirconium,

Compounds of Formula (II):

Bis(cyclopentadienyl)dimethylzirconium,

bis(cyclopentadienyl)diphenylzirconium,

bis(cyclopentadienyl)diethylzirconium,

bis(cyclopentadienyl)dibenzylzirconium,

bis(cyclopentadienyl)dimethoxyzirconium,

bis(cyclopentadienyl)dichlorolzirconium,

bis(cyclopentadienyl)dihydridezirconium,

bis(cyclopentadienyl)monochloromonohydridezirconium,

bis(methylcyclopentadienyl)dimethylzirconium,

bis(methylcyclopentadienyl)dichlorozirconium,

bis(methylcyclopentadienyl)dibenzylzirconium,

bis(pentamethylcyclopentadienyl)dimethylzirconium,

bis(pentamethylcyclopentadienyl)dichlorozirconium,

bis(pentamethylcyclopentadienyl)dibenzylzirconium,

bis(pentamethylcyclopentadienyl)chloromethylzirconium,

bis(pentamethylcyclopentadienyl)hydridemethylzirconium,

(cyclopentadienyl)(pentamethylcyclopentadienyl)dichlorozirconium.

Compounds of Formula (III):

Ethylenebis(indenyl)dimethylzirconium,

ethylenebis(indenyl)dichlorozirconium,

ethylenebis(tetrahydroindenyl)dimethylzirconium,

ethylenebis(tetrahydroindenyl)dichlorozirconium,

dimethylsilylenebis(cyclopentadienyl)dimethylzirconium,

dimethylsilylenebis(cyclopentadienyl)dichlorozirconium,

isopropyl(cyclopentadienyl)(9-fluorenyl)dimethylzirconium,

isopropyl(cyclopentadienyl)(9-fluorenyl)dichlorozirconium,

[phenyl(methyl)methylene](9-fluorenyl)(cyclopentadienyl)dimethylzirconium,

diphenylmethylene(cyclopentadienyl)(9-fluorenyl)dimethylzirconium,

ethylidene(9-fluorenyl)(cyclopentadienyl)dimethylziroconium,

cyclohexylidene(9-fluorenyl)(cyclopentadienyl)dimethylzirconium,

cyclopentylidene(9-fluorenyl)(cyclopentadienyl)dimethylzirconium,

cyclobutylidene(9-fluorenyl)(cylcopentadienyl)dimethylzirconium,

dimethylsilylene(9-fluorenyl)(cyclopentadienyl)dimethylzirconium,

dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl)dichlorozirconium,

dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl)dimethylzirconium,

dimethylsilylenebis(indenyl)dichlorozirconium.

Further, compounds other than the cyclopentadienyl compound representedby Formula (I), (II) or (III) can be used. Examples of such compoundsinclude those compounds represented Formula (IV) [Compound (A1)], suchas tetramethylzirconium, tetrabenzylzirconium, tetramethoxyzirconium,tetraethoxyzirconium, tetrabutoxyzirconium, tetrachlorozirconium,tetrabromozirconium, butoxytrichlorozirconium,dibutoxydichlorozirconium, bis(2,5-di-t-butylphenoxy)dimethylzirconium,bis(2,5-di-t-butylphenoxy)dichlorozirconium and zirconiumbis(acetylacetonate).

In the present invention, olefin based polymers can be produced in thepresence of a catalyst comprising as main components this Compound (A1)and Compound (B), without using Compound (C).

Further, in the present invention, as Compound (A), a IVB Grouptransition metal compound having a ligand which is a multidentate ligandcompound wherein two substituted or unsubstituted conjugatedcycloalkadienyl groups (provided that at least one group is asubstituted cycloalkadienyl group) are connected to each other throughan element selected from the IVA Groups of the Periodic Table, can bepreferably used. Using this compound, isotactic polyolefins having highisotacticity, high molecular weight and high melting point can beproduced.

Such compounds include, for example, those represented by the followingFormula (V) or their derivatives. ##STR1##

In Formula (V), Y is a carbon, silicon, germanium or tin atom; and R⁵_(t) --C₅ H_(4--t) and R⁵ _(u) --C₅ H_(4--u) are independently asubstituted cyclopentadienyl group; t and u are an integer of 1 to 4. R⁵is a hydrogen atom, silyl group or hydrocarbon group, and may be thesame as or different from each other. Further, in at least onecyclopentadienyl ring, R⁵ is connected to at least one carbon atomlocated next to a carbon atom connected to Y. R⁶ is a hydrogen atom,C₁₋₂₀ alkyl group, C₆₋₂₀ aryl group, alkylaryl group or arylalkyl group.M² is a Ti, Zr or Hf atom. X is a hydrogen atom, halogen atom, C₁₋₂₀alkyl group, C₆₋₂₀ aryl group, alkylaryl group or arylalkyl group, orC₁₋₂₀ alkoxy group. X may be the same as or different from each otherand two R⁶ are the same as or different from each other.

In Formula (V), the substituted cycopentadienyl groups include, forexample, a methylcyclopentadienyl group, ethylcyclopentadienyl group,isopropylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group,1,3-dimethylcyclopentadienyl group, 1,2,3-trimethylcyclopentadienylgroup and 1,2,4-trimethylcyclopentadienyl group. Examples of X includehalogen atoms such as a fluorine atom, chlorine atom, bromine atom andiodine atom; C₁₋₂₀ alkyl groups such as a methyl group, ethyl group,n-propyl group, isopropyl group, n-butyl group, octyl group and2-ethylhexyl group; C₁₋₂₀ alkoxy groups such as a methoxy group, ethoxygroup, propoxy group, butoxy group and phenoxy group; and C₆₋₂₀ arylgroups, alkylaryl groups or arylalkyl groups, such as a phenyl group,tolyl group, xylyl group and benzyl group. Examples of R⁶ are, forexample, a methyl group, ethyl group, phenyl group, tolyl group, xylylgroup and benzyl group.

These compounds (V) include, for example, the following compounds, andthose having titanium or hafnium instead of zirconium.Dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride, dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl)hafniumdichloride.

In the present invention, syndiotactic polyolefins having highsyndiotacticity and high molecular weight can be produced by using thefollowing compound (A2) of the above Formula (III ) as the transitionmetal compound (A). Compound (A2) represented by the following Formula(VI):

    (Cp.sup.1 --Ae--Cp.sup.2)M.sup.1 R.sup.1 fR.sup.2 g        (VI)

wherein Cp¹ is a cyclopentadienyl group or substituted cyclopentadienylgroup; Cp² is a fluorenyl group or substituted fluorenyl group; A is abridge based on a covalent bond; e is an integer of 0 to 6; M¹ is atransition metal slected from the IVB Group of the Periodic Table; R¹and R² may be the same as or different from each other, and areindependently a ligand having a sigma bond, chelate ligand or Lewisbase; and f and g are independently an integer of 0 to 2 .

In the Compound (A2), the substituted cyclopentadienyl group (Cp¹)includes, for example, a methylcyclopentadienyl group,ethylcyclopentadienyl group, isopropylcyclopentadienyl group,1,2-dimethylcyclopentadienyl group, tetramethylcyclopentadienyl group,1,3-dimethylcyclopentadienyl group, 1,2,3-trimethylcyclopentadienylgroup, 1,2,4-trimethylcyclopentadienyl group, pentamethylcyclopentadieylgroup and trimethylsilylcyclopentadienyl group.

The substituted fluorenyl group (Cp²) includes, for example, alkylfluorenyl groups such as 2-methylfluorenyl group and3,6-dimethylfluorenyl group.

The substituents contained in the substituted cyclopentadienyl groupsare preferably alkyl groups having 1 to 6 carbon atoms. The number ofthe substituents attached may be selected from an integer of 1 to 4.Further, the substituents contained in the substituted fluorenyl groupsare preferably alkyl groups having 1 to 6 carbon atoms. The number ofthe substituents attached may be selected from an integer of 1 to 4.

The bridges based on a covalent bond, A include, for example, amethylene bridge, dimethylmethylene bridge, ethylene bridge,dialkylsilylene bridge (alkyl having 1 to 4 carbon atoms) such as adimethylsilylene bridge, dimethylgelmylene bridge, dimethylstannylenebridge, diphenylmethylene bridge, phenylmethylmethylene bridge,cyclohexylidene bridge, cyclopentylidene bridge, cyclobutylene bridge,methylcyclohexylidene bridge, isopropylmethylmethylene bridge andt-butylmethylmethylene bridge.

M¹ is a transition metal selected from the IVB Group of the PeriodicTable, i.e., titanium (Ti), zirconium (Zr), hafnium (Hf) or the like.

R¹ and R² are independently a ligand having a sigma bond, a chelateligand or a Lewis base ligand, such as a hydrogen atom, halogen atom,C₁₋₂₀ alkyl group, C₁₋₂₀ alkoxy group, C₆₋₂₀ aryl group, C₆₋₂₀ aryloxygroup alkylaryl group or arylalkyl group, C₁₋₂₀ acyloxy group, allylgroup, substituted allyl group, acetylacetonate group, substitutedacetylacetonate group, substituent having a silicon atom, carbonyl,oxygen molecule, nitrogen molecule, Lewis base, chain unsaturatedhydrocarbon, or cylic unsaturated hydrocarbon. R¹ and R² may connectwith each other to form a ring.

Examples of R¹ and R² include as a halogen atom F, Cl, Br and I; C₁₋₂₀alkyl groups such as a methyl group, ethyl group, n-propyl group,isopropyl group, n-butyl group, octyl group and 2-ethylhexyl group;C₁₋₂₀ alkoxy groups such as a methoxy group, ethoxy group, propoxygroup, butoxy group C₆₋₂₀ aryloxy groups such as a phenoxy group; C₆₋₂₀aryl groups, alkylaryl groups or arylalkyl group, such as a phenylgroup, tolyl group, xylyl group and benzyl group; C₁₋₂₀ acyloxy groupssuch as a heptadecylcarbonyloxy group; substituents containing a siliconatom such as a trimethylsilyl group and (trimethylsilyl)methyl group;Lewis bases such as ethers including dimethyl ether, diethyl ether andtetrahydrofuran, thioethers including tetrahydrothiophen, estersincluding ethylbenzoate, nitriles including acetonitrile andbenzonitrile, amines including trimethylamine, triethylamine,tributylamine, N, N-dimethylaniline, 2,2'-bipyridine andphenantholorine, and phosphines including triethylphosphine andtriphenylphosphine; chain unsaturated hydrocarbons such as ethylene,butadiene, 1-pentene, isoprene, pentadiene, 1-hexene; unsaturated cyclichydrocarbons such as benzene, toluene, xylene, cycloheptatriene,cyclooctadiene, cyclooctatriene, cyclooctatetraene.

More specifically, these compounds (A2) include the following compounds,and those having titanium or hafnium instead of zirconium:

(Arylalkylidene)(9-fluorenyl)(cyclopentadienyl)zirconium dimethyl,(diarylmehtylene)(9-fluorenyl)(cyclopentadienyl)zirconium dimethyl,(cycloalkylidene)(9-fluorenyl)(cyclopentadienyl)zirconium dimethyl,

(dialkylmethylene)(9-fluorenyl)(cyclopentadienyl)zirocnium dimethyl,(dialkylsilylene)(9-fluorenyl)(cyclopentadienyl)zirconium dimethyl and(dialkylmethylene)(9-fluorenyl)(cyclopentadienyl)zirconium dichloride.Particularly suitable compounds are[methyl(phenyl)methylene](9-fluorenyl)(cyclopentadienyl)zirconiumdimethyl,

(diphenylmethylene)(9-fluorenyl)(cyclopentadienyl)zirconium dimethyl,ethylene(9-fluorenyl)(cyclopentadienyl)zirconium dimethyl,(cyclohexylidene)(9-fluorenyl)(cyclopentadienyl)zirconium dimethyl,(cyclopentylidene)(9-fluorenyl)(cyclopentadienyl)zirconium dimethyl,

(cyclobutylidene)(9-fluorenyl)(cyclopentadienyl)zirconium dimethyl and(dimethylsilylene)(9-fluorenyl)(cyclopentadienyl)zirconium dimethyl.

In the present invention, Compound (A2) which can be preferably used mayhave Bridge A containing at least one substituent which is not a methylgroup, particularly bridges represented by the following Formula (VII):##STR2## wherein B is a carbon, silicon, germanium or tin atom; R^(x)and R^(y) may be same as or different from each other, and areindependently a hydrogen atom, halogen atom, hydrocarbon atom or alkoxygroup, provided that at least one of R^(x) and R^(y) is not a methylgroup; and R^(x) and R^(y) may form a ring. If these compounds are usedas Compound (A2), the resultant homopolymers or copolymers may have highmolecular weight and narrow molecular weight distribution.

In addition, among transition metal compounds (A), the transition metalcompounds containing a transition metal belonging to the VIII Group ofthe Periodic Table, include chromium compounds such astetramethylchromium, tetra(t-butoxy)chromium,bis(cyclopnetadienyl)chromium andhydridetricarbonyl(cyclopentadienyl)chromium; manganese compounds suchas tricarbonyl(cyclopentadienyl)manganese, pentacarbonylmethylmanganese,bis(cyclopentadienyl)manganese and manganese bis(acetylacetonate);nickel compounds such as dicarbonylbis(triphenylphosphine)nickel,dibromobis(triphenylphosphine)nickel,dinitrogenbis(bis(tricyclohexylphosphine)nickel) andchlorohydridebis(tricyclohexylphosphine)nickel; and palladium compoundssuch as dichlorobis(benzonitrile)palladium,carbonyltris(triphenylphosphine)palladium,dichlorobis(triethylphosphine)palladium and bis(isocyanatedt-butyl)palladium.

Further, Compounds (B) are not particularly limited to, but include anycompounds capable of forming an ionic complex when reacted with thetransition metal compound (A). The suitable compounds as Compounds (B)include a compound comprising a cation and an anion wherein a pluralityof functional groups are connected to an element, particularly acoordination complex compound comprising a cation and an anion wherein aplurality of covalently coordinated groups are connected to an elementselected from the Groups of VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA andVA of the Periodic Table. The suitable compounds comprising a cation andan anion wherein a plurality of covalently coordinated groups areconnected to an element, include, for example, those compoundsrepresented by the following Formula (VIII) or (IX):

    ([L.sup.1 --R.sup.7 ].sup.k+).sub.p ([M.sup.3 Z.sup.1 Z.sup.2 . . . Z.sup.n ].sup.(n--m)--).sub.q                                     (VIII)

    ([L.sup.2 ].sup.k+).sub.p ([M.sup.4 Z.sup.1 Z.sup.2 . . . Z.sup.n ].sup.(n--m)--).sub.q                                     (IX)

wherein L² is M⁵, R⁸ R⁹ M⁶, R¹⁰ ₃ C or R¹¹ M⁶. In Formula (VIII) or(IX), L¹ is a Lewis base; M³ and M⁴ are independently an elementselected from the groups of VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA andVA, preferably IIIA, IVA and VA, of the Periodic Table; M⁵ and M⁶ areindependently an element selected from the groups of IIIB, IVB, VB, VIB,VIIB, VIII, IA, IB, IIA, IIB and VIIA of the Periodic Table; Z¹ to Z^(n)are independently a hydrogen atom, dialkylamino group, C₁₋₂₀ alkoxygroup, C₆₋₂₀ aryloxy group, C₁₋₂₀ alkyl group, C₆₋₂₀ aryl group,alkylaryl group or arylalkyl group, C₁₋₂₀ halogenated hydrocarbon group,C₁₋₂₀ acyloxy group, organometalloid group or halogen atom; two or moreof Z¹ to Z^(n) may form a ring; R⁷ is a hydrogen atom, C₁₋₂₀ alkylgroup, C⁶⁻²⁰ aryl group, alkylaryl group or arylalkyl group; R⁸ and R⁹are independently a cyclopentadienyl group, substituted cyclopentadienylgroup, indenyl group or fluorenyl group; R¹⁰ is a C¹⁻²⁰ alkyl group,aryl group, alkylaryl group or arylalkyl group; R¹¹ is a large ringligand such as tetraphenylporphyrin and phthalocyanine; m is a valencyof M³ and M⁴ and is an integer of 1 to 7; n is an integer of 2 to 8; kis an ion value number of [L¹ -R⁷ ] and [L² ], and is an integer of 1 to7; and p is an integer of at least 1; and q is specified by the formula:q=(p×k)/(n-m).

Examples of the above Lewis bases are amines such as ammonia,methylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, tri-n-butylamine,N,N-dimethylaniline, methyldiphenylamine, pyridine,p-bromo-N,N-dimethylaniline and p-nitro-N,N-dimethylaniline; phosphinessuch as triethylphosphine, triphenylphosphine and diphenylphosphine;ethers such as dimethyl ether, diethyl ether, tetrahydrofuran anddioxane; thioethers such as diethyl thioethers and tetrahydrothiophene;and esters such as ethylbenzoate. Examples of M³ and M⁴ are, forexample, B, Al, Si, P, As and Sb, preferably B and P. Examples of M⁵ areLi, Na, Ag, Cu, Br, I and I₃. Examples of M⁶ are Mn, Fe, Co, Ni and Zn.Examples of Z¹ to Z^(n) include dialkylamino groups such as adimethylamino group and diethylamino group; C₁₋₂₀ alkoxy groups such asa methoxy group, ethoxy group and n-butoxy group; C₆₋₂₀ aryloxy groupssuch as phenoxy group, 2,6-dimethylphenoxy group and naphthyloxy group;C₁₋₂₀ alkyl groups such as a methyl group, ethyl group, n-propyl group,iso-propyl group, n-butyl group, n-octyl group and 2-ethylhexyl group;C₆₋₂₀ aryl, alkylaryl or arylalkyl groups, such as a phenyl group,p-tolyl group, benzyl group, 4-t.-butylphenyl group, 2,6-dimethylphenylgroup, 3,5-dimethylphenyl group, 2,4-dimethylphenyl group,2,3-dimethylphenyl group; C₁₋₂₀ halogenated hydrocarbon groups such asp-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group,3,4,5-trifluorophenyl group, pentafluorophenyl group,3,5-di(trifluoromethyl)phenyl group; halogen atoms such as F, Cl, Br andI; and organometalloid groups such as a pentamethylantimony group;trimethylsilyl group, trimethylgelmyl group, diphenylarsine group,dicyclohexylantimony group and diphenylboron group. Examples of R⁷ andR¹⁰ are the same as above. Examples of substituted cyclopentadienylgroups represented by R⁸ and R⁹ include those substituted with an alkylgroup such as a methylcyclopentadienyl group, butylcyclopentadienylgroup and pentamethylcyclopentadienyl group. Usually, the alkyl groupshave 1 to 6 carbon atoms and the number of substituted alkyl groups isan integer of 1 to 5. In Formula (VIII) or (IX), M³ and M⁴ arepreferably boron.

Of those compounds represented by Formula (VIII) or (IX), the followingcompounds can be particularly used as preferred ones.

Compounds Represented by Formula (VIII):

Triethylammonium tetraphenylborate, tri(n-butyl)ammoniumtetraphenylborate, trimethylammonium tetraphenylborate,tetraethylammonium tetraphenylborate, methyltri(n-butyl)ammoniumtetraphenylborate, benzyltri(n-butyl)ammonium tetraphenylborate,dimethyldiphenylammonium tetraphenylborate, methyltriphenylammoniumtetraphenylborate, trimethylanilinium tetraphenylborate,methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate,methyl(2-cyanopyridinium) tetraphenylborate, trimethylsulfoniumtetraphenylborate, benzyldimethylsulfonium tetraphenylborate,triethylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, triphenylammoniumtetrakis(pentafluorophenyl)borate, tetrabutylammoniumtetrakis(pentafluorophenyl)borate, tetraethylammoniumtetrakis(pentafluorophenyl)borate, methyltri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, benzyltri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, methyldiphenylammoniumtetrakis(pentafluorophenyl)borate, methyltriphenylammoniumtetrakis(pentafluorophenyl)borate, dimethyldiphenylammoniumtetrakis(pentafluorophenyl)borate, aniliniumtetrakis(pentafluorophenyl)borate, methylaniliniumtetrakis(pentafluorophenyl)borate, dimethylaniliniumtetrakis(pentafluorophenyl)borate, trimethylaniliniumtetrakis(pentafluorophenyl)borate, dimethyl(m-nitroanilinium)tetrakis(pentafluorophenyl)borate, dimethyl(p-bromoanilinium)tetrakis(pentafluorophenyl)borate, pyridiniumtetrakis(pentafluorophenyl)borate, p-cyanopyridiniumtetrakis(pentafluorophenyl)borate, N-methylpyridiniumtetrakis(pentafluorophenyl)borate, N-benzylpyridinium tetrakis(pentafluorophenyl)borate, O-cyano-N-mehtylpyridiniumtetrakis(pentafluorophenyl)borate, p-cyano-N-methylpyridiniumtetrakis(pentafluorophenyl)borate, p-cyano-N-benzylpyridiniumtetrakis(pentafluorophenyl)borate, trimethylsulfoniumtetrakis(pentafluorophenyl)borate, benzyldimethylsulfoniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, tetraphenylphosphoniumtetrakis(pentafluorophenyl)borate, dimethylaniliniumtetrakis(3,5-ditrifluoromethylphenyl)borate, and hexafluoroarsenic acidtriethylammonium.

Compounds Represented by Formula (IX):

Ferrocenium tetraphenylborate, silver tetraphenyl borate, trityltetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate,ferrocenium tetrakis(pentafluorophenyl)borate, 1,1'-dimethylferroceniumtetrakis(pentafluorophenyl)borate, decamethylferroceniumtetrakis(pentafluorophenyl)borate, acetylferroceniumtetrakis(pentafluorophenyl)borate, formylferroceniumtetrakis(pentafluorophenyl)borate, cyanoferroceniumtetrakis(pentafluorophenyl)borate, silvertetrakis(pentafluorophenyl)borate, trityltetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, sodiumtetrakis(pentafluorophenyl)borate, tetraphenylporphyrin manganesetetrakis(pentafluorophenyl)borate, tetra(pentafluorophenyl)boric acid(tetraphenylporphyrin iron chloride), tetrakis(pentafluorophenyl)boricacid (tetraphenylporphyrin zinc), tetrafluorosilver borate,hexafluoroarsenical silver, and hexafluorosilver antimonate.

Further, compounds other than those represented by Formula (VIII) or(IX) such as tris(pentafluorophenyl)boron,tris(3,5-di(trifluoromethyl)phenyl)boron and triphenylboron, can be alsoused.

Organic aluminum compounds as Component (C) include those represented bythe following formula (X), (XI) or (XII):

    R.sup.12.sub.r AlQ.sub.3--r                                (X)

wherein R¹² is a hydrocarbon group such as an alkyl group, alkenylgroup, aryl group or arylalkyl group having 1 to 20, preferably 1 to 12carbon atoms; Q is a hydrogen atom, a C₁₋₂₀ alkoxy group or a halogenatom; and r is a number between 1 and 3.

Examples of compounds represented by Formula (X) are, for example,trimethylaluminum, triethylaluminum, triisopropylaluminum,triisobutylaluminum, dimethylaluminum chloride, diethylaluminumchloride, methylaluminum dichloride, ethylaluminum dichloride,dimethylaluminum fluoride, diisobutylaluminum hydroide, diethylaluminumhydride and ethylaluminumsesquichloride.

Chain aluminoxanes represented by the following Formula (XI): ##STR3##wherein R¹² is as defined in Formula (X); and s is a degree ofpolymerization, usually from 3 to 50, preferably 7 to 40.

Cyclic alkylaluminoxanes having a repeating unit represented by theformula: ##STR4## wherein R¹² is defined in Formula (X); and s is adegree of polymerization, usually from 3 to 50, preferably 7 to 40.

Of these compounds represented by Formulas (X) to (XII), preferablecompounds are an aluminum compound containing at least one alkyl grouphaving at least three carbon atoms, particularly a branched alkyl groupand aluminoxanes. Particularly preferred are triisobutylaluminum andaluminoxanes with a polymerization degree of at least 7. Use oftriisobutylaluminum, aluminoxane with polymerization degree of at least7 or a mixture thereof gives higher activity than use oftrimethylaluminum or triethylaluminum.

Methods of preparing the above aluminoxanes are not particularly limitedto, but include any known methods such as a process comprisingcontacting alkylaluminum with a condensation agent such as water.Alkylaluminum and a condensation agent can be reacted by known methods,for example, (1) a method comprising dissolving an organoaluminumcompound in an organic solvent, and contacting the solution with water;(2) a method comprising adding an organoaluminum compound to startingmaterials for polymerization, and adding water to the reaction mixturelater; (3) a method comprising reacting an organoaluminum compound withcrystalline water contained in a metal salt and the like or wateradsorbed to an inorganic material or an organic material; (4) a methodcomprising reacting tetraalkyldialuminoxane with trialkylaluminum, andthen reacting the reaction product with water.

Catalysts which can be used in the present invention comprise, as mainingredients, the above Components (A), (B) and (C). Further, thecatalysts comprising, as main ingredients, Component (A1) as Component(A) and Component (B) can be used.

In this case, the use conditions are not limited; however it ispreferable to adjust a ratio (molar ratio) of Component (A) to Component(B) to 1:0.01 to 1:100, more preferably 1:0.5 to 1:10, most preferably1:1 to 1:5. Further, reaction temperature may preferably range from-100° to 250° C. Reaction pressure and reaction time can beappropriately selected.

Further, the amount of Component (C) used may be from 0 to 2,000 moles,preferably from 5 to 1,000 moles, most preferably from 10 to 500 moles,per 1 mol of Component (A). The use of Component (C) may improvepolymerization activity. However, the use of excess amount of Component(C) is not desirable since a great amount of the organoaluminum compoundwill remain in the resultant polymer.

In addition, a way of using the catalysts is not particularly limited.For example, it is possible that Components (A) and (B) are preliminaryreacted and the reaction product is separated, washed and used forpolymerization. It is also possible that Components (A) and (B)themselves are contacted in a polymerization system. Further, Component(C) can be contacted with Component (A), Component (B), or the reactionproduct of Component (A) and Component (B). These components can becontacted before polymerization or during polymerization. Further, thesecomponents can be added to monomers or a solvent before polymerization,or to the polymerization system.

In the present invention, an alpha-olefin can be homo-polymerized, ortwo or more of alpha-olefins can be co-polymerized in theabove-mentioned polymerization system.

In this case, the alpha-olefins are not particularly limited to, butinclude those represented by the following Formula (XlII):

    R.sup.13 --CH═CH.sub.2                                 (X)

wherein R¹³ is an alkyl group having 1 to 28, preferably 2 to 20, carbonatoms.

More specifically, suitable alpha-olefins include, for example,ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-hexene,4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,1-hexadecene, 1-octadecene and 1-eicosene.

In the present invention, when two or more of alpha-olefins arecopolymerized, any combination of the above monomers can be used.However, it is particularly preferable to copolymerize ethylene and analpha-olefin having 3 to 10 carbon atoms. In this case, a molar ratio ofethylene to the other alpha-olefin may be 99.9:0.1 to 0.1:99.9.

In the present invention, in addition to the above alpha-olefins, it ispossible to copolymerize a small amount of other unsaturated compoundssuch as vinyl aromatic compounds such as styrene, p-methylstyrene,isopropylstyrene and t-butylstyrene, and chain diolefins such asbutadiene, isoprene and 1,5-hexadiene. In general, the other unsaturatedcompounds are used in an amount of 20 mole percent based on the amountof the alpha-olefin used. In this case, at least one alpha-olefin ispreferably used.

Polymerization methods are not particularly limited to, but include bulkpolymerization, solution polymerization, suspension polymerization andgas phase polymerization. In addition, either of a batch process or acontinuous process can be used.

As for polymerization conditions, the polymerization temperature mayrange from -100° to 250° C., preferably from -50° to 200° C. Further,the catalyst is preferably used in an amount to provide a startingmonomer/Component (A) molar ratio or a starting monomer/Component (B)molar ratio of from 1 to 10⁹, preferably from 100 to 10⁷. Thepolymerization time may usually range from 1 minute to 10 hours. Thereaction pressure may range from normal pressure to 100 Kg/cm² G,preferably from normal pressure to 50 Kg/cm² G.

The molecular weight of the resultant polymer can be controlled byappropriately selecting the amount of each catalyst component andpolymerization temperature, or by a polymerization reaction in thepresence of hydrogen.

In the case of using polymerization solvents, suitable solvents includearomatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene;alicyclic hydrocarbons such as cyclopentane, cyclohexane andmethylcyclohexane; aliphatic hydrocarbons such as pentane, hexane,heptane and octane; and halogenated hydrocarbons such as chloroform anddichloromethane. These solvents can be used alone or in combination.Monomers such as alpha-olefins can also be used as solvent.

EXAMPLES

The present invention will be described in more detail with reference tothe following Examples and Comparative Examples, which are not used tolimit the present invention.

In the Examples and Comparative Examples, physical properties weremeasured as follows.

Mw, Mn, Mw/Mn

In Examples 1 to 16, these were measured at 135° C. by the GelPermeation Chromatography (GPC) using 1,2,4-trichlorobenzene as asolvent and polyethylene as standard polymer.

In Examples 17 to 28, these were measured at 135° C. by GPC using1,2,4-trichlorobenzene as a solvent and polystyrene as standard polymer.

Melting Point (Tm)

The melting point was measured by DSC analysis.

Intrinsic Viscosity [η]

The intrinsic viscosity was measured in decalin at 135° C.

Propylene Content

The propylene content was measured by ¹³ C-NMR.

Octene Content

The octene content was measured by ¹ H-NMR.

Syndiotactic Index

The syndiotactic index was measured by ¹³ C-NMR.

EXAMPLE 1

(1) Synthesis of [Cp₂ Fe][B(C₆ F₅)₄ ] (synthesized in accordance withtechniques described in Jolly, W. L. The Synthesis and Characterizationof Inorganic Compounds; Prentice-Hall: Englewood Cliffs, N.J., 1970,P487):

Ferrocene (3.7 g, 20.0 mmol) was reacted with 40 ml of concentratedsulfuric acid at room temperature for one hour to obtain very dark bluesolution. The obtained solution was placed in 1 litter of water withagitation to obtain slightly dark blue solution. The obtained solutionwas added to 500 ml of an aqueous solution of Li[B(C₆ F₅)₄ ] (13.7 g,20.0 mmol: Synthesized in accordance with a process described in J.Organometal. Chem., 2 (1964) 245). The light blue precipitate was takenby filtaration and then washed with 500 ml of water five times. Then,the washed product was dried under reduced pressure to obtain 14.7 g ofthe target product, [ferrocenium tetrakis(pentafluorophenyl)borate.

(2) Ethylene Polymerization:

A 1 litter autoclave which was dried and purged with nitrogen, wascharged with 400 ml of toluene, 0.2 mmol of triisobutylaluminum, 0.01mmol of the ferrocenium tetrakis(pentafluorophenyl)borate obtained asabove, 0.01 mmol of bis(cyclopentadienyl)dimethylzirconium. Then, thepolymerization was carried out at 60° C. for 1 hour while ethylene wascontinuously introduced so as to keep an inner pressure to 10 Kg/cm². Asa result, 180 g of polyethylene were obtained. The polymerizationactivity per 1 g of aluminum used, was 33 Kg/gAl.

The obtained polymer had a Mw of 193,000 and a Mw/Mn of 3.99.

EXAMPLE 2

The procedures of Example 1 were repeated except thatehylenebis(indenyl)dimethylzirconium was used instead ofbis(cyclopentadienyl)dimethylzirconium; ethylene 10 Kg/cm² was changedto propylene 7 Kg/cm² ; the polymerization temperature was changed to30° C.; and the polymerization time was changed to 1 hour. As a result,10.3 g of polypropylene were obtained.

It was confirmed by IR and ¹³ C-NMR that the obtained polymer wasisotactic polypropylene.

In addition, the obtained polymer had a Mw of 23,000, a Mw/Mn of 2.64and a melting point of 142.6° C.

EXAMPLE 3

The procedures of Example 2 were repeated except that 1 Kg/cm² ofpropylene was introduced instead of 7 Kg/cm² of propylene; and ethylenewas continuously added to keep an inner pressure of 2 Kg/cm². As aresult, 14.0 g of an ethylene/propylene copolymer were obtained.

It was confirmed that the obtained product was a copolymer since a broadmelting point at around 90° C. was observed by DSC analysis.

In addition, the obtained copolymer had a propylene content of 35.0 mol%, a Mw of 54,000 and a Mw/Mn of 3.27.

EXAMPLE 4

The procedures of Example 1 were repeated except that 0.01 mmol oftetrabenzylzirconium were used instead of 0.01 mmol ofbis(cyclopentadienyl)dimethylzirconium; and the polymerization time waschanged to 3 hours. As a result, 48 g of polyethylene were obtained.

The obtained polymer had a Mw of 286,000 and a Mw/Mn of 3.35.

EXAMPLE 5

The procedures of Example 4 were repeated except thatbis(2,5-di-t-butylphenoxy)dimethylzirconium was used instead oftetrabenzylzirconium. As a result, 35 g of polyethylene were obtained.

The obtained polymer had a Mw of 355,000 and a Mw/Mn of 3.50.

EXAMPLE 6

A one litter continuous type autoclave was charged with toluene as asolvent at 1 litter/hr, ethylene and propylene at an ethylene/propyleneratio of 29/71 (molar ratio) at a flow rate of 3.75 litter/min. and, ascatalyst components, bis(cyclopentadienyl)zirconium dimethyl at 0.01mmol/hr, ferrocenium tetrakis(pentafluorophenyl)borate at 0.01 mmol/hrand triisobutylaluminum at 0.2 mmol/hr. Then polymerization was carriedout at 55° C. while the total pressure was controlled to keep 8 Kg.cm².

As a result, an ethylene/propylene copolymer was obtained at a rate of72 g/hr. The polymerization activity per 1 g of aluminum used, was 13.3Kg/gAl.

In addition, the obtained copolymer had an intrinsic viscosity of 0.60dl/g and a propylene content of 32.3 wt. %.

COMPARATIVE EXAMPLE 1

The procedures of Example 1 were repeated except thattriisobutylaluminum was not used; and the polymerization time waschanged to 3 hours.

As a result, 0.04 g of a polymer were obtained.

COMPARATIVE EXAMPLE 2

The procedures of Example 1 were repeated except that ferroceniumtetrakis(pentafluorophenyl)borate was not used; and the polymerizationtime was changed to 3 hours.

As a result, a polymer was not obtained.

COMPARATIVE EXAMPLE 3

The procedures of Example 1 were repeated except that 0.2 mmol ofaluminoxane (degree of polymerization: 20) were used instead of 0.2 mmolof triisobutylaluminum; and ferroceniumtetrakis(pentafluorophenyl)borate was not used.

As a result, 7 g of a polymer were obtained.

EXAMPLE 7

(1) Preparation ofDimethylsilylenebis(2,3,5-trimethylcyclopentadienyl)dichlorozirconium:

In a 300 ml glass reaction vessel, 7.2 g ofdimethylbis(2,3,5-trimethylcyclopentadienyl)silane were dissolved in 100ml of tetrahydrofuran. To the obtained solution, 52.8 ml of a hexanesolution of n-butyllithium were added dropwise at 0° C. The solution wasfurther stirred at room temperature for 3 hours to obtain yellowsuspension.

Further, in a 500 ml glass reaction vessel, zirconium tetrachloride wascooled to -78° C. and dichloromethane was added. To this, the previouslithium salt was added dropwise to heat to room temperature. Then, theheat refluxing was carried out for 40 hours. After cooling, theprecipitate portion was removed to concentrate the yellow solution.Then, a light yellow solid was obtained by addition of hexane. Theobtained solid was subjected to recrystallization fromdichloromethane/hexane to obtain 0.4 g of a white crystal ofdimethylsilylbis(2,3,5-trimethylcyclopentadienyl)zirconium dichlorid.

(2) Propylene Polymerization:

A two litter autoclave sufficiently purged with nitrogen, was chargedwith 400 ml of toluene, 0.01 mmol of triisobutylalumihum, 0.005 mmol offerrocenium tetrakis(pentafluoro)borate and 0.005 mmol ofdimethylsilyl(2,3,5-trimethylcyclopentadienyl)zirconium dichloride.Propylene was introduced into the autoclave to keep a total pressure of3 Kg.cm². Then, the polymerization was carried out for 2 hours. Afterreaction, the catalyst components were decomposed by methanol and theobtained polymer was dried, to obtain 20.0 g of isotactic polypropylene.

The polymerization activity was 22 Kg/gZr. In addition the obtainedpolymer had a Mw of 120,000 and a melting point of 162.0° C.

Comparative Example 4

A two litter autoclave sufficiently purged with nitrogen, was chargedwith 400 ml of toluene, 0.005 mmol of ferroceniumtetrakis(pentafluoro)borate and 0.005 mmol ofdimethylsilyl(2,3,5-trimethylcyclopentadienyl)zirconium dichloride.Propylene was introduced into the autoclave to keep a total pressure of3 Kg.cm². Then, the polymerization was carried out for 2 hours. Afterreaction, the catalyst components were decomposed by methanol. However,almost no polymer was obtained.

EXAMPLE 8

(1) Preparation of Dimethylanilinium

Tetrakis(pentafluorophenyl)borate:

Pentafluorophenyllithium prepared from 152 mmol ofbromopentafluorobenzene and 152 mmol of butyllithium was reacted with 45mmol of boron trichloride in hexane, to obtaintri(pentafluorophenyl)boron as a white solid product.

The obtained tris(pentafluorophenyl)boron (41 mmol) was reacted with 41mmol of pentafluorophenyllithium, to isolate lithiumtetrakis(pentafluorophenyl)borate as a white solid product.

Thereafter, lithium tetrakis(pentafluorophenyl)borate (16 mmol) wasreacted with dimethylaniline hydrochloride (16 mmol) in water, to obtain11.4 mmol of dimethylanilinium tetrakis(pentafluorophenyl)borate as awhite solid product.

It was confirmed by ¹ H-NMR and ¹³ C-NMR that the reaction product wasthe target product.

(2) Copolymerization of Ethylene/1-Octene

A one litter autoclave which was dried and purged with nitrogen, wascharged with 400 ml of toluene, 0.6 mmol of triisobutylaluminum, 6 μmolof bis(cyclopentadienyl)zirconium dichloride, and 6 μmol ofdimethylanilinium tetrakis(pentafluorophenyl)borate obtained in Step (1)above in this order. Then, 31 mmol (0.2 mol) of octene were added. Afterthe reaction mixture was heated to 70° C. the polymerization was carriedout for 30 minutes while continuously introducing ethylene so as to keepthe ethylene partial pressure to 3 Kg/cm². As a result, 72.1 g of anethylene/1-octene copolymer were obtained.

The polymerization activity was 132 Kg/gZr. In addition, the obtainedcopolymer had an octene content of 2 mol %; a density of 0.919 g/cm² ;an intrinsic viscosity of 1.89 dl/g, a Mw of 90,600, a Mw/Mn of 2.15 anda melting point of 112° C.

EXAMPLE 9

The procedures of Example 8 were repeated except that triethylaluminum(0.6 mmol) was used instead of triisobutylaluminum (0.6 mmol) in thepolymerization, to obtain 5.7 g of an ethylene/1-octene copolymer.

The polymerization activity was 10.0 Kg/gZr. In addition, the obtainedcopolymer had an octene content of 1.5 mol %, an intrinsic viscosity of3.27 dl/g and a melting point of 120° C.

EXAMPLE 10

A one litter autoclave was charged with 400 ml of toluene, 1.0 mmol oftriisobutylaluminum, 6 μmol of zirconium tetrachloride and 9 μmol ofdimethylanilinium tetrakis(pentafluorophenyl)borate in this order. Then,31 mmol (0.2 mol) of octane were added. After the reaction mixture washeated to 90° C., the polymerization was carried out for 30 minuteswhile continuously introducing ethylene so as to keep the ethylenepartial pressure to 9 Kg/cm². As a result, 7.35 g of anethylene/1-octene copolymer were obtained.

The polymerization activity was 13 Kg/gZr. In addition, the obtainedcopolymer had an octene content of 1 mol %; an intrinsic viscosity of6.05 dl/g and a melting point of 126° C.

EXAMPLE 11

The procedures of Example 9 were repeated except that 6 μmol oftetrabutoxyzirconium were used instead of zirconium tetrachloride in thepolymerization, to obtain 1.88 g of an ethylene/1 -octene copolymer.

The polymerization activity was 13 Kg/gZr. In addition, the obtainedcopolymer had an octene content of 1 mol %, an intrinsic viscosity of2.87 dl/g and a melting point of 131° C.

EXAMPLE 12

The procedures of Example 9 were repeated except that 6 μmol oftetrabenzylzirconium were used instead of zirconium tetrachloride in thepolymerization, to obtain 10.3 g of an ethylene/1 -octene copolymer.

The polymerization activity was 19 Kg/gZr. In addition, the obtainedcopolymer had an octene content of 3 mol %, an intrinsic viscosity of2.61 dl/g and a melting point of 105° C.

EXAMPLE 13

The procedures of Example 9 were repeated except that 9 μmol of hafniumtetrachloride was used instead of zirconium tetrachloride in thepolymerization, to obtain 7.09 g of an ethylene/1-octene copolymer.

The polymerization activity was 4.41 Kg/gZr. In addition, the obtainedcopolymer had an octene content of 2 mol %, an intrinsic viscosity of6.57 dl/g and a melting point of 130° C.

EXAMPLE 14

The procedures of Example 9 were repeated except that octene was notused; after heating to 90° C., propylene was introduced to keep itspartial pressure of 2 Kg/cm², and then ethylene was introduced to keepits partial pressure of 7 Kg/cm² in the copolymerization. As a result,2.4 g of an ethylene/propylene copolymer were obtained.

The polymerization activity was 4.39 Kg/gZr. In addition, the obtainedcopolymer had a propylene content of 12 mol %, an intrinsic viscosity of2.91 dl/g and a melting point of 129° C.

EXAMPLE 15

A one litter autoclave which was dried and purged with nitrogen, wascharged with 400 ml of toluene, 1 mmol of triisobutylaluminum, 0.01 mmolof tetrabenzylzirconium and 0.01 mmol of tris(pentafluorophenyl)boron.Then, the polymerization was carried out at an inner temperature of 80°C. for 1 hour while continuously introducing ethylene into the autoclaveso as to keep the ethylene partial pressure to 7 Kg/cm². As a result,0.65 g of polyethylene were obtained.

The polymerization activity was 0.71 Kg/gZr. In addition, the obtainedpolymer had an intrinsic viscosity of 7.24 dl/g.

EXAMPLE 16

The procedures of Example 15 were repeated except that 0.01 mmol ofdimethylanilinium tetrakis(pentafluorophenyl)borate were used instead oftris(pentafluorophenyl)boron, to obtain 18.09 g of polyethylene.

The polymerization activity was 20 Kg/gZr. In addition, the obtainedcopolymer had an intrinsic viscosity of 7.88 dl/g.

EXAMPLE 17

The procedures of Example 16 were repeated except that 1 mmol oftriethylaluminum was used instead of triisobutylaluminum; and thepolymerization time was changed to 20 minutes in the polymerization. Asa result, 12.26 g of polyethylene were obtained.

The polymerization activity was 13 Kg/gZr. In addition, the obtainedcopolymer had an intrinsic viscosity of 4.11 dl/g.

EXAMPLE 18

The procedures of Example 16 were repeated except that 1 mmol ofmethylaluminoxane (degree of polymerization: 20) was used instead oftriisobutylaluminum in the polymerization. As a result, 16.3 g ofpolyethylene were obtained.

The polymerization activity was 18 Kg/gZr. In addition, the obtainedcopolymer had an intrinsic viscosity of 7.27 dl/g.

EXAMPLE 19

A one litter autoclave which was dried and purged with nitrogen, wascharged with 400 ml of toluene, 0.1 mmol of tetrabenzylzirconium and 0.1mmol of dimethylanilinium tetrakis(pentafluorophenyl)borate. Then, thepolymerization was carried out at an inner temperature of 80° C. for 90minutes while continuously introducing ethylene into the autoclave so asto keep the ethylene partial pressure to 9 Kg/cm². As a result, 0.94 gof polyethylene were obtained.

The polymerization activity was 0.10 Kg/gZr. In addition, the obtainedpolymer had an intrinsic viscosity of 2.44 dl/g.

EXAMPLE 20

(1) Synthesis of [Cp₂ Fe][B(C₆ F₅)₄ ]:

In the same manner as in Example 1 (1), ferroceniumtetrakis(pentafluorophenyl)borate was synthesized.

(2) Polymerization:

A stainless autoclave was charged with 30 ml of dried toluene, 0.002mmol of the ferrocenium tetrakis(pentafluorophenyl)borate obtained asabove, and 0.002 mmol ofmethylphenylmethylene(cyclopentadienyl)zirconium dimethyl. Then, 500 mlof liquid propylene was added and the polymerization was carried out at70° C. for 1 hour. As a result, 0.5 g of syndiotactic polypropylene wereobtained. The polymerization activity was 2.7 Kg/gZr.

The obtained syndiotactic polypropylene had a Mw of 311,000, a Mn of135,000, a Mw/Mn of 2.3 and a syndiotactic index (racemi-diad) of 94%.

EXAMPLE 21

A stainless autoclave was charged with 30 ml of dried toluene, 0.1 mmolof triisobutylaluminum, 0.002 mmol of the ferroceniumtetrakis(pentafluoro-phenyl)borate obtained as above, and 0.002 mmol ofmethylphenylmethylene(cyclopentadienyl)zirconium dimethyl. Then, 500 mlof liquid propylene were added and the polymerization was carried out at70° C. for 1 hour. As a result, 22 g of syndiotactic polypropylene wereobtained. The polymerization activity was 121 Kg/gZr.

The obtained syndiotactic polypropylene had a Mw of 485,000, a Mn of211,000, a Mw/Mn of 2.3 and a syndiotactic index (racemi-diad) of 95%.

EXAMPLE 22

The procedures of Example 21 were repeated except that 0.002 mmol ofdiphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl wereused instead ofmethylphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl.As a result, 28 g of syndiotactic polypropylene were obtained. Thepolymerization activity was 154 Kg/gZr.

The obtained syndiotactic polypropylene had a Mw of 453,000, a Mn of162,000, a Mw/Mn of 2.8 and a syndiotactic index (racemi-diad) of 96%.

EXAMPLE 23

The procedures of Example 21 were repeated except that 0.002 mmol ofcyclohexylidene(1,1-cyclopentadienyl)(9-fluorenyl)zirconium dimethylwere used instead ofmethylphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl.As a result, 25 g of syndiotactic polypropylene were obtained. Thepolymerization activity was 137 Kg/gZr.

The obtained syndiotactic polypropylene had a Mw of 525,000, a Mn of210,000, a Mw/Mn of 2.5 and a syndiotactic index (racemi-diad) of 96%.

EXAMPLE 24

The procedures of Example 23 were repeated except that 0.002 mmol oftriethylammonium tetrakis(pentafluorophenyl)borate were used instead offerrocenium tetrakis(pentafluorophenyl)borate. As a result, 23 g ofsyndiotactic polypropylene were obtained. The polymerization activitywas 126 Kg/gZr.

The obtained syndiotactic polypropylene had a Mw of 420,000, a Mn of150,000, a Mw/Mn of 2.8 and a syndiotactic index (racemi-diad) of 94%.

EXAMPLE 25

The procedures of Example 23 were repeated except that thepolymerization temperature was changed from 70° C. to 40° C., to obtain3.5 g of syndiotactic polypropylene. The polymerization activity was 19Kg/gZr.

The obtained syndiotactic polypropylene had a Mw of 895,000, a Mn of280,000, a Mw/Mn of 3.2 and a syndiotactic index (racemi-diad) of 98%.In addition, the melting point was 145° C.

EXAMPLE 26

The procedures of Example 22 were repeated except that 0.002 mmol ofdiphenylmethylene(cyclopentadienyl)(9-fluorenyl)hafnium dimethyl wereused instead ofdiphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl. As aresult, 22 g of syndiotactic polypropylene were obtained. Thepolymerization activity was 62 Kg/gHf.

The obtained syndiotactic polypropylene had a Mw of 513,000, a Mn of160,000, a Mw/Mn of 3.2 and a syndiotactic index (racemi-diad) of 95%.

EXAMPLE 27

A stainless autoclave was charged with 30 ml of dried toluene, 0.1 mmolof triisobutylaluminum and 0.002 mmol ofmethylphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconiumdichloride. After sufficient agitation, 0.002 mmol of Li[B(C₆ F₅)₄ ]were added and 500 ml of liquid propylene were further added. Then, thepolymerization was carried out at 70° C. for 1 hour. As a result, 10 gof syndiotactic polypropylene were obtained. The polymerization activitywas 54 Kg/gZr.

The obtained syndiotactic polypropylene had a Mw of 420,000, a Mn of150,000, a Mw/Mn of 2.8 and a syndiotactic index (racemi-diad) of 93%.

EXAMPLE 28

A glass reaction vessel was charged with 50 ml of 4-methyl-1-pentene,0.2 mmol of triisobutylaluminum, 0.01 mmol of aniliniumtetrakis(pentafluorophenyl)borate and 0.01 mmol ofisopropyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride. Then, thepolymerization was carried out at 20° C. for 90 hours. As a result, 7.6g of syndiotactic poly(4-methyl-1-pentene) were obtained. Thepolymerization activity was 8.3 Kg/gZr.

The obtained syndiotactic polypropylene had a Mw of 24,000, a Mn of10,000, a Mw/Mn of 2.4, a syndiotactic index (racemi-pentad) of 91% anda melting point of 204° C.

FIG. 2 shows the results of measurement of NMR[¹³ C{H}] for the obtainedpolymer. From the peak at 31.249 ppm in FIG. 2, it was found that theobtained polymer was a syndiotactic polymer.

EXAMPLE 29

The procedures of Example 28 were repeated except that 0.01 mmol ofisopropyl(cyclopentadienyl)(9-fluorenyl)hafnium dichloride were usedinstead of isopropyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride.As a result, 3.5 g of syndiotactic poly(4-methyl-1-pentene) wereobtained. The polymerization activity was 2.0 Kg/gHf.

The obtained polymer had a Mw of 32,000, a Mn of 12,000, a Mw/Mn of 2.7,a syndiotactic index (racemi-pentad) of 90% and a melting point of 202°C.

EXAMPLE 30

The procedures of Example 28 were repeated except that 20 mmol of3-methyl-1-butene were used instead of 4-methyl-1-pentene, to obtain 2.3g of syndiotactic poly(3-methyl-1-butene) were obtained. Thepolymerization activity was 2.5 Kg/gZr.

The obtained polymer had a Mw of 22,000, a Mn of 8,800, a Mw/Mn of 2.5,a syndiotactic index (racemi-pentad) of 90% and a melting point of 229°C.

FIG. 3 shows the results of measurement of NMR[¹³ C{H}] for the obtainedpolymer. From the peak at 29.295 ppm in FIG. 3, it was found that theobtained polymer was a syndiotactic polymer.

EXAMPLE 31

The procedures of Example 28 were repeated except that 0.01 mmol ofphenyl(methyl)methylene(cyclopentadienyl)(9-fluorenyl)zirconiumdichloride were used instead ofisopropyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride. As aresult, 4.0 g of syndiotactic poly(4-methyl-1-pentene) were obtained.The polymerization activity was 2.2 Kg/gHf.

The obtained polymer had a Mw of 40,000, a Mn of 19,000, a Mw/Mn of 2.1,a syndiotactic index (racemi-pentad) of 92% and a melting point of 210°C.

EXAMPLE 32

A glass reaction vessel was charged with 50 ml of 4-methyl-1-pentene,0.2 mmol of methylaluminoxane, 0.01 mmol of aniliniumtetrakis(pentafluorophenyl)borate and 0.01 mmol ofisopropyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride. Then, thepolymerization was carried out at 20° C. for 90 hours. As a result, 7.0g of syndiotactic poly(4-methyl-1-pentene) were obtained. Thepolymerization activity was 7.7 Kg/gZr.

EXAMPLE 33

A glass reaction vessel was charged with 50 ml of 4-methyl-1-pentene,0.2 mmol of triethylaluminoxane, 0.01 mmol of aniliniumtetrakis(pentafluorophenyl)borate and 0.01 mmol ofisopropyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride. Then, thepolymerization was carried out at 20° C. for 90 hours. As a result, 1.0g of syndiotactic poly(4-methyl-1-pentene) was obtained. Thepolymerization activity was 1.1 Kg/gZr.

EXAMPLE 34

The procedures of Example 22 were repeated except that 0.002 mmol ofdiphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl wereused instead ofdiphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl. As aresult, 120 g of atactic polypropylene were obtained.

We claim:
 1. A process for producing an olefin based polymer in whichpolymerization of one or more alpha-olefins of formula (XIII)

    R.sup.13 --CH═CH.sub.2

wherein R¹³ is a hydrogen atom or an alkyl group having from 1 to 28carbon atoms, is carried out in the presence of a catalyst comprisingthe compounds (A) and (B): (A) a transition metal compound (A1)represented by the following formula:

    M.sup.1 R.sup.1 aR.sup.2 bR.sup.3 cR.sup.4 d

wherein M¹ is Ti, Zr or Hf, R¹, R², R³ and R⁴ are each independentlyhydrogen, oxygen, halogen, C₁₋₂₀ alkyl, C₁₋₂₀ alkoxy, C₆₋₂₀ aryl, C₆₋₂₀aryloxy, alkylaryl, arylalkyl, C₁₋₂₀ acyloxy, allyl, trialkylsilyl,ether, thioether, ester, nitrile, amine, phosphine or acetylacetonate;a, b, c and d are each independently an integer of from 0 to 4; and twoor more of R¹, R², R³ and R⁴ may form a ring; and (B) a compound capableof forming an ionic complex when reacted with said transition metalcompound.
 2. The process of claim 1, wherein said catalyst furthercomprises compound (C) an organoaluminum compound.
 3. The processaccording to claim 2, wherein said organoaluminum compound (C) is amember selected from the group consisting of organoaluminum compoundscontaining at least one alkyl group having at least three carbon atomsand aluminoxanes.